Polynitro nitrate compounds and method of preparation



This invention relates to new and useful polynitro nitrates and a method for their preparation. Inparticu lar it relates to aliphatic polynitro nitrates having the general formula: Y

wherein A is an alkylene radical and Z is a nitromethylene, dinitromethylene or nitramine radical.

The nitro compounds of this invention are useful as high explosives and can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge. An example of such a missile is disclosed in U.S. Patent No. 2,470,162, issued May 17, 1949. One way of using the high explosives in a device such as that disclosed in U.S. Patent No. 2,470,162 is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufficiently insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellent charge, and can be caused to explode on operation of an impactor time-fuse mechanism firing a detonating explosive such as lead azide or mercury fulminate.

The compounds of this invention are readily prepared by reacting the corresponding alcohols with nitric acid, in accordance with the general reaction scheme set forth below:

wherein A and Z are as defined above.

The nitro alcohols used as starting materials in this invention are readily prepared by the reduction of the corresponding acyl halides with sodium borohydride, as disclosed in assignees copending application No. 392,- 471, now abandoned, filed November 16, 1953.

To more clearly illustrate this invention, the following examples are presented. It is to be understood, however, that these examples are presented merely as a means of illustration and are not intended to limit the scope of the invention in any way.

EXAMPLE I Preparation of 4,4,6,8,8-pentanitr-1,II-undecane dinitmte The solid 4,4,6,8,8-pentanitro-l,1l-undecanediol was added to a tenfold excess of 100% commercial nitric acid at ice-bath temperature. The acid solution was stirred for a period of 15 minutes at a temperature of about 5- l0 C. and then poured over ice. The white solid was collected, washed with water and dried in vacuum over potassium hydroxide. The product was recrystallized from methanol in 96.1% yield and exhibited a melting atent I l 3,000,920 Patented Sept. 19, 1961 ice point of 73-75 "7 C. 'I'heelemental analysis of the compound is as follows:

Calculated f0I C1 H17N 1O15Z C, 26.25%; H, 3.41%; N, 19.48%. Found: C, 26.79%; H, 3.64%; N, 19.18%.

- Prep tzrat iori of 4,4,6,6,8,8-hexiinitro-1,II-undecane di trate By reacting 4,4,6,6,8,8 hexanitro 1,11 -undecanediol with nitric acid in'accordance with'the procedure in Example I, 4,4,6,6,8,8-hexanitro-1,lleundecane dinitrate 1 having a melting point of 100l01 C. was obtained in 95.2% yield. The elemental analysis of the product is as follows:

Calculated for C11H18N3013: C, H, N, 20.44%. Found: C, 24.54%; H, 2.99%; N, 19.91%. The explosive values of the product were calculated to be:

Lead block value 138 T.N.T.=

Ballistic mortar value 143 T.-N.T.= 100 EXAMPLE III Preparation of 4,4,6,8,8-pentaititro-6-aza-1,II-undecane dinitrate By reacting 4,4,6,8,8-pentanitro-6-aza-1,1l-undecanediol with nitric acid in accordance with the procedure in Example I, 4,4,6,8,8-pentanitro-6-aza-1,1l-undecane di-. nitrate having a melting point of 133-135 C. was obtained in 95.0% yield. The elemental analysis of the product is as follows:

Calculated for C H N O C, 23.82%; H, 3.20%; N, 22.22%. Found: C, 23.88%; H, 2.96%; N, 22.15%. The explosive values of the product were calculated to be:

Lead block value 135 T.N.T.= 100 Ballistic mortar value 142 T.N.T.-=100 I have also'found that the homologues of the above compounds, namely, 3,3,5,5,7,7-hexanitro-1,9-nonanediol, 3,3,5,7,7-pentanitro-1,9-nonanediol and 3,3,5,7,7-pentanitro-5-aza-1,9-nonanediol also react with nitric acid forming the nitrate esters 3,3,5,5,7,7-hexanitro-l,9-nonane dinitrate, 3,3,5,7,7-pentanitro-1,9-nonane dinitrate, and 3,3,5,7,7-pentanitro-5-aza-1,9-nonane dinitrate.

It is apparent that any member of the nitro-containing aliphatic nitrate series may be prepared by merely selecting the appropriate nitro-containing alcohol and reacting it with nitric acid, in accordance with the teachings of this invention.

This application is a continuation-in-part of my copending U.S. Patent Application Ser. No. 409,263, now abandoned, filed February 9, 1954.

I claim:

1 As compositions of matter, the aliphatic polynitronitrates having the formula:

wherein A is a lower alkylene radical and Z is a radical selected from the group consisting of nitromethylene, dinitromethylene and nitramine radicals.

2. As a composition of matter, 4,4,6,8,8-pentanitro-1, 11-undecane dinitrate having the structural formula:

0 11001 If): ITIO; N Or-CHzCHzCHa-C-CHr-CH-CHz-Ei-CHaCHaCHrN 03 N O: NO:

. t V 3 3. As a composition of matter, 4,4,6,6,8,8-hexanitro- 1",1'1'undecane' dinit'rate having the structural formula:

4. As acomposition of matter, 4,4,6,8-,8-pehtani;tro-6- aza-1,-1l-undecane dinitrate having the structural formula:

I 5. The method-0f preparingaliphatic polynitronitrates having the formula:

which comprises reacting nitric acid with a nitro-confai'nin'g'dioi havirig the formula:

wherein A is a lower alkylene radical and Z is a member of a group consisting of nit'mmethylene, dinitrom'ethylene' and nitramine radicals.

6. The method of. preparing 4,4,6,8,8pentanitro-I,11- undeca'n'e dinitra'te which comprises reacting 4,4,6,8,8- pentanitro-1,1l-undecariediol with nitric acid.

7. The method of preparing- 4,4,6 6,8,8-hexanitro=1',11- undecane dinitra-te which comprises reacting 4,4,6,6,8,8- hexanitro-Ll l-undecanediol ;withnitric acid.

8. The method of preparing 4,4,6,8,8-pentanitro-6 aza- 1,11-undecane dinitrate which comprises reacting 4,4,6,8, 8-pentanitro-6-aza-Lll-undecanediol with nitric acid.

No references cited. 

1. AS COMPOSITIONS OF MATTER, THE ALIPHATIC POLYNITRONITRATES HAVING THE FORMULA: 